Spin-transition parent compounds

ABSTRACT

A chemical composition is provided for the manufacture of devices for storing and/or displaying information, comprising a network having a molecule which is formed from a metallic element Fe (II)  which is bonded to a 1-2-4 triazole ligand (H-Trz), which molecule further comprises one or more than one anions A selected from BF 4   − , ClO 4   − , CO 3   2− , Br − , Cl − , in accordance with the formulation: 
     
       
         Fe II  (H-Trz) 3 A 2 , 
       
     
     characterized in that this composition is used in the pure state in either one of the two crystalline phases (α, β) at least one of which, referred to as the second phase (β), can be thermally induced on the basis of the other phase, referred to as the first phase (α), at a temperature which is equal to or higher than a first reference temperature (To), which phases each show thermally inducible spin transitions between a low-spin state at a low first temperature (T α1 , T β1 ) and a high-spin state at a high second temperature (T α2 , T β2 ), the spin transitions which are associated with each phase being accompanied by a similar abrupt change in color of the compound and taking place in accordance with hysteresis cycles at different temperatures of the two phases, wherein the hysteresis cycle (T α1 , T α2 ) associated with the first phase (α) occurs at a temperature which is higher than a second reference temperature (T R ), and the hysteresis cycle (T β1 , T β2 ) associated with the second phase (β) occurs at a temperature below the second reference temperature (T R ), the first reference temperature (To) being higher than the second reference temperature (T R ) and the highest spin-transition temperature (T α2 ).

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of application Ser. No. 08/383,170,filed Feb. 3, 1995, now U.S. Pat. No. 6,043,008, which is acontinuation-in-part of application Ser. No. 08/247,383 filed May 23,1994, now U.S. Pat. No. 5,582,900, which is a continuation-in-part ofapplication Ser. No. 07/979,104, filed Nov. 20, 1992, now abandoned.

Spin-transition parent compounds and devices having means for writing,storing and erasing, which comprise an active medium containing at leastone of said compounds.

The invention relates to spin-transition parent compounds and to methodsof manufacturing said compounds.

The invention also relates to devices having means for writing, storingand erasing, which comprise an active medium containing at least one ofsaid parent compounds. The invention further relates to methods ofutilizing these devices.

The invention is used in the field of information storage and processingdevices and/or data display devices.

In Patent Application EP-0 543 465, there is already disclosed a familyof compounds which can suitably be used to form materials which can bewritten and erased by means of heat and whose operating rangecorresponds to the ambient temperature range.

This family is formed from a network of molecules, comprising:

A) a metal, such as iron Fe_(II) or Fe_(III), or cobalt Co_(II),

B) ligands which are bonded to this metal, such as:

a substituted 1-2-4 triazole of the abridged formula R-Trz, wherein R isan alkyl C_(n) H_(2n+1)

a 1-2-4 triazolate of the abridged formula Trz⁻

C) an anion which is selected from the group formed by BF₄ ⁻, ClO₄ ⁻,CO₃ ²⁻, Br⁻, Cl⁻

D) and at least one water molecule H₂O which is not covalently bonded tothe metal complex, but whose presence in the network can be attributedto an hygroscopic agent selected from the precursors of the metalnucleus,

E) and a doping agent, which is an aminotriazole of the abridged formulaR′-Trz, wherein R′ is an amine N—C_(n)H_(2n+1)

The general formula of the molecules of the family described in theabove-mentioned document can be expressed as follows:

M_(II)[(R-Trz)₂(Trz⁻)]_(1−x) (R′-Trz)_(x) A, n H₂O.

In this formula, M is the metal and A is the anion,

and substituted triazole types, the respective proportions of which aregoverned by the value x of the concentration,

and n is the number of water molecules H₂O which are bonded in anon-covalent manner to the molecule of the metal complex.

In addition, in this formula the concentration value x is small, so thatthe proportion of the ligand R′-Trz is small and, in fact, constitutes adoping agent which acts on the intrinsical properties of the material.

The above-mentioned, exemplary molecules which are selected from saidgeneral family include:

Fe_(II)[(HTrz)₂(Trz⁻)]_(0.9) (NH₂-Trz)_(0.1) (BF₄ ⁻), 6H₂O

wherein

NH₂-Trz is aminotriazole which is used as a dopant.

A method of preparing compounds of this general family consists incombining a salt of the metal (for example Fe(ClO₄ ⁻)₂) with the ligandsin an acid solution, thereby forming a precipitate. Subsequently, theprecipitate is separated from the solution. Said precipitate is obtainedin powdered form. By using an excess of the metal salt, a certainquantity of water is captured.

The compounds of the general family described in EP 0 543 465 exhibitspin transitions, between a low-spin state (LS) and a high-spin state(HS), which are induced only by heat, and which involve electronic andstructural changes of the molecules. Said changes bring about an abruptchange of the absorption spectrum of the molecules and hence of thecolour of the compounds, and the electronic energy levels also beingdifferent.

In the low-spin state (LS), the compounds are dark purple, whereas inthe high-spin state (HS), these compounds are chalk-white. In addition,each of the high-spin (HS) and low-spin (LS) states is perfectly stableif the compounds are subjected to an average temperature, referred to asaverage critical temperature, which ranges between the maximum andminimum temperatures in the high-spin state or low-spin state.

Studies of these materials have revealed that, apart from spintransition, they exhibit a delay effect which can be attributed tointermolecular cooperativity, resulting in a hysteresis phenomenonwhich, dependent upon the material used, may range from several degreescentigrade to several tens of degrees centigrade, between −20 and 100°C., i.e. in a temperature range which is appropriate for industrialapplications.

When a thermal perturbation is applied, the cooperative effect bringsabout that either:

all molecules simultaneously undergo a transition within an aggregate,

or none of the molecules undergoes said transition.

The compounds of the general family disclosed in EP 0 543 465 can alsobe used as memory materials which can be thermally written and erasedand optically read and, thus, can also be used to store information,process information or display information.

The document in accordance with the state of the art EP 0 543 465,discloses that the temperature range in which the compounds operatedepends to a substantial extent on the properties of the ligand selectedas the dopant.

The spin transition of the known compounds presupposes the existence oftwo potential wells, one of which corresponds to the low-spin state (LS)and the other corresponds to the high-spin state (HS). These potentialwells are separated by a potential barrier. The bottom of each of thepotential wells corresponds, respectively, to a first and a secondenergy level, the energy level of the bottom of the high-spin well beinghigher than the energy level of the bottom of the low-spin well.

The application of a thermal perturbation to one of the compounds ofsaid family, which has first been brought to a stable low-spin state(LS) in which the electrons are trapped in the first potential well,results in the induction of unstable, excited high-spin states, afterwhich the electrons relax via allowed transitions, while following aprincipal relaxation path, being the path of the second potential well,which corresponds to a perfectly stable high-spin state in a specifictemperature range. The electrons remain trapped in the second potentialwell corresponding to the high-spin state (HS) and do not spontaneouslyreturn to the first potential well corresponding to the low-spin state(LS) due to the hysteresis phenomenon. To return to the low-spin state(LS), the compound must be cooled to a temperature which lies wellwithin the hysteresis range.

Meanwhile, the compounds of the family known from the above-mentioneddocument exhibit too small a hysteresis amplitude in the ambienttemperature range in which they are to be used as materials forrecording or storing information. For example, exemplary compound No.5of EP 0 543 465

Fe_(II)[(HTrz)₂(Trz⁻)]_(0.9) (NH₂-Trz)_(0.1) (BF₄ ⁻), 6H₂O

has a critical temperature in the range from 20 to 25° C. and ahysteresis amplitude of only 10 to 20°.

It is an object of the invention to provide compounds which are selectedfrom compounds which:

present thermally induced spin transitions and hence can be thermallywritten and erased,

can be optically read,

exhibit stable spin states,

have a critical temperature in the ambient temperature range,

exhibit a hysteresis effect which has a much larger amplitude than thatof the compounds of the above-mentioned document EP 0 543 465, so that abetter control of both the writing and erasing operations is possibleand, in particular, the temperatures at which writing or erasing takeplace meet the standards imposed by the manufacturers of displaydevices, said standards being:

T≦5° C. for erasing

T>50° C. for writing.

These objects are achieved by means of a spin-transition parent compoundin powder form, comprising a network having a molecule which is formedfrom a complex in which iron (Fe_(II)) is bonded to a 1-2-4 triazoleligand (H-Trz), said molecule further comprising an anion (A)₂ which isselected from BF₄ ⁻, ClO₄ ⁻, Br⁻, CO₃ ²⁻, and, dependent upon the anion,said molecule corresponding to the formula:

a) Fe_(II)(H-Trz)₃ (BF₄ ⁻)₂

b) Fe_(II)(H-Trz)₃ (ClO₄ ⁻)₂

c) Fe_(II)(H-Trz)₃ (Br⁻)₂

d) Fe_(II)(H-Trz)₃ (Cl⁻)₂

e) Fe_(II)(H-Trz)₃ (CO₃ ²⁻)

In an alternative embodiment in accordance with the the invention, thereis proposed a spin-transition parent compound in powder form, comprisinga network having a molecule which is formed from a complex in which iron(Fe_(II)) is bonded to a 1-2-4 triazole ligand (H-Trz), said moleculefurther comprising an anion (A)₂ which is selected from BF₄ ⁻, ClO₄ ⁻,Br⁻, ClO₃ ²⁻, and, dependent upon the anion, said molecule correspondingto the formula:

a) Fe_(II)(H-Trz)₃ (BF₄ ⁻)₂, H₂O

b) Fe_(II)(H-Trz)₃ (ClO₄ ⁻)₂, H₂O

c) Fe_(II)(H-Trz)₃ (Br⁻)₂, H₂O

d) Fe_(II)(H-Trz)₃ (Cl⁻)₂, H₂O

e) Fe_(II)(H-Trz)₃ (CO₃ ²⁻), H₂O

wherein one water molecule per molecule of the iron complex is presentin the network, said water molecule only being bonded to the 1-2-4triazole ligand (H-Trz) by a hydrogen bond.

This parent compound has a surprising effect, which is not known to beproduced by the general family described in European Patent ApplicationEP 0 543 465. Said surprising effect consists in that the parentcompound in accordance with the invention has two crystalline phases(α,β) at least one of which, referred to as the second phase (β), can bethermally induced on the basis of the other phase, referred to as thefirst phase (α), at a temperature which is equal to or higher than afirst reference temperature (To). Said surprising effect is notdescribed in EP 0 543 465 and, in accordance with the invention, thecompounds of the general family, excluding those selected herein to formthe present parent compound, do not produce this effect.

These two crystalline phases (α,β) each exhibit thermally inducible spintransitions between a low-spin state at a low first temperature (T_(α2),T_(β2)) and a high-spin state at a high second temperature (T_(α1),T_(β1)), said spin transitions which are associated with each phasebeing accompanied by an abrupt change in colour of the compound betweena first colour and a second colour, which changes in colour are the samefor both phases. Said spin transition of each phase takes place inaccordance with hysteresis cycles at temperatures which are differentfor each of the two phases. The hysteresis cycle (T_(α1), T_(α2))associated with the first phase (α) occurs at a temperature which ishigher than a second reference temperature (T_(R)), and the hysteresiscycle (T_(β1), T_(β2)) associated with the second phase (β) occurs at atemperature below the second reference temperature (T_(R)), the firstreference temperature (To) being higher than the second referencetemperature (T_(R)) and the highest spin-transition temperature(T_(α1)).

These novel and unexpected properties enable this parent compound to beused more satisfactorily in the preparation of active media forinformation display devices, information storage devices and informationprocessing devices.

The invention will be explained in greater detail with reference to theaccompanying schematic drawings, in which

FIG. 1 shows the enthalpy H which corresponds to the spin transition ofa quantity of a compound, for example 1 mole, as a function of arbitrarymolecular coordinates, for example the metal-ligand distance D;

FIG. 2 shows the hysteresis cycles, corresponding to each of the statesot and β, of compounds in accordance with the invention, wherein X,being the molar fraction of the material which has undergone atransition at the temperature T, is plotted on the Y-axis and T, beingthe temperature in degrees Kelvin, is plotted on the X-axis;

FIG. 3 show the different stages of writing, storing or erasing by meansof the compounds in accordance with the invention.

I CHEMICAL FORMULATION OF THE PARENT COMPOUNDS SELECTED IN ACCORDANCEWITH THE INVENTION

In accordance with the invention, a description is given of a sub-familyof compounds selected from the general family of compounds disclosed inPatent Application EP 0 543 465. The terms “spin-transition compounds”and “spin-transition parent compounds” are used interchangeably todenote the products selected in accordance with the invention from saidgeneral family.

As stated hereinabove, the compounds of the known general family exhibitspin-transition properties and a hysteresis phenomenon between thelow-spin state (LS) and the high-spin state (HS). The criticaltemperature of the known compounds lies in the ambient temperaturerange, at approximately 20° C., but they have a small hysteresisamplitude, typically, of approximately 10 degrees.

The hysteresis amplitude of the compounds between their low-spin state(LS) and high-spin state (HS) is expanded by means of the followingselection of compounds.

It has been found that the compounds in accordance with the invention,which are selected from the general family, exhibit novel and unexpectedproperties.

However, in order to obtain these properties the selected compounds mustbe prepared in accordance with a specific method of manufacture.

The selected compounds comprise a molecule which is formed from acomplex of iron Fe_(II) in which said metal Fe_(II) is bonded to a 1-2-4triazole ligand of the following formula

This molecule further comprises an anion which is selected from:

BF₄ ⁻, ClO₄ ⁻, Br⁻, Cl⁻, CO₃ ²⁻.

Dependent upon the selected anion, these compounds have the followingformula:

a) Fe_(II)(A-TrZ)₃ (BF₄ ⁻)₂

b) Fe_(II)(H-Trz)₃ (ClO₄ ⁻)₂

c) Fe_(II)(H-Trz)₃ (Br⁻)₂

d) Fe_(II)(H-Trz)₃ (Cl⁻)₂

e) Fe_(II)(H-Trz)₃ (CO₃ ²⁻)

In these compounds, a molecule can allow a water molecule H₂O to bepresent, resulting in the following chemical formulation of thecompounds:

a′) Fe_(II)(H-Trz)₃ (BF₄ ⁻)₂, H₂O

b′) Fe_(II)(H-Trz)₃ (ClO₄ ⁻)₂, H₂O

c′) Fe_(II)(H-Trz)₃ (Br⁻)₂, H₂O

d′) Fe_(II)(H-Trz)₃ (Cl⁻)₂, H₂O

e′) Fe_(II)(H-Trz)₃ (CO₃ ²⁻), H₂O

The presence of said water molecule per molecule of the compound is notindispensable. When said water molecule is present, it is situated inthe network, but it is not covalently bonded to the elements of thechemical formulas a′), b′), c′), d′), e′). This water molecule is onlybonded by a hydrogen bond to the H-Trz ligand, i.e. the 1-2-4 triazole.When this water molecule is present, it acts on the metal-ligand bondingstrength.

To ensure that said water molecule is present in the network, use mustbe made of a specific method of manufacture.

II METHOD OF MANUFACTURING COMPOUNDS HAVING THE PRECEDING CHEMICALFORMULATION

For example, to prepare the compound whose chemical formula correspondsto a) Fe_(II)(H-Trz)₃ (BF₄ ⁻)₂, the following constituents are mixed:

n moles of Fe(BF₄)₂, 6H₂O, which is a salt which is used as a precursoraround the central iron Fe_(II) atom, in a solution of pure methanolCH₃—Oh, in a concentration of 10 n moles per litre;

and 3n moles of 1-2-4 triazole in a solution of pure methanol CH₃—OH, ina concentration of 30 n moles per litre, at ambient temperature, i.e.approximatley 20 to 25° C.

In this method of manufacture, n is a number which is greater than zero.

This mixture is subsequently concentrated under a vacuum, for example ata pressure of approximately 30 mm of mercury, i.e. 4.10³ Pa (760mm.Hg=10⁵ Pa) while simultaneously bringing this mixture to atemperature in the range between 60 and 80° C., for example,approximately 70° C.

A compound of formula a) Fe_(II)(H-Trz)₃ (BF₄ ⁻)₂ precipitates veryrapidly.

As soon as the precipitate is obtained, it is important to eliminate themethanol solvent as quickly as possible, for example by filtering, toobtain an at least 99 wt. % pure compound.

The compound of the formula Fe_(II)(H-Trz)₃ (BF₄ ⁻)₂ thus obtained ispreserved without washing it or subjecting it to other treatments.

To obtain a water molecule in the network, which leads to a compound ofthe formula:

a′) Fe(H-Trz)₃ (BF₄ ⁻)₂, H₂O an excess of the precursor of iron, Fe(BF₄⁻)₂, 6H₂O, can be used. Instead of n moles of Fe(BF₄ ⁻)₂, 6H₂O, for 3 nmoles of 1-2-4 triazole, use can be made, for example, of 2 n or 3 nmoles of Fe(BF₄ ⁻)₂, 6H₂O.

To avoid an excess of iron caused by using an excess of the precursor ofiron, which can adversely affect the optical and magnetic properties inthe case of oxidation, hygroscopic salts, such as Mg(ClO₄)₂, K CLO₄,NaCIO₄, can be added in a quantity of 25 to 100 wt. % instead of anexcess of the precursor of iron.

In this manufacturing process, those skilled in the art must take carethat the methanol solvent is removed completely and rapidly as soon asthe precipitate is obtained. In fact, if the molecule Fe(H-Trz)₃ (BF₄⁻)₂ remains in contact with a small quantity of, for example, several mlof methanol solvent, said molecule is “deprotonated”, which results in acompound of the formula:

Fe(Trz⁻)(H-Trz)(BF₄ ⁻),

wherein the metal Fe_(II) is bonded to two ligands, (Trz⁻) and (H-Trz),instead of to the single ligand (H-Trz). It is noted that Trz⁻ is 1-2-4triazolate.

Thus, the method of preparation which is preferred in accordance withthe invention enables the following pure compound to be obtained:

Fe(H-Trz)₃(BF₄ ⁻)₂

wherein the metal Fe_(II) is bonded to the single 1-2-4 triazole ligand(HTrz). If those skilled in the art do not produce the compound by meansof an appropriate method, a mixture of:

Fe(Trz⁻)(H-Trz)₂ (BF₄ ⁻) [compound having two ligands (Trz⁻) and(H-Trz)]

 +Fe(H-Trz)₃ (BF₄ ⁻)₂, [compound in accordance with the invention]

is always obtained, in which mixture the main constituent is thecompound having two ligands, which comprises triazolate and which hasthe following formula

Fe(Trz⁻)(H-Trz)₂(BF₄ ⁻).

When the above mixture is obtained, the main compound Fe(Trz⁻)(H-Trz)₂(BF₄ ⁻) masks the properties of the compound Fe(H-Trz)₃ (BF₄ ⁻)₂ which,consequently, is an “impurity”.

However, it is just the compound Fe(H-Trz)₃ (BF₄ ⁻)₂ which exhibits thesurpising properties in accordance with the invention described herein.Consequently, it is important to obtain this product with the highestpossible degree of purity, i.e. the compound exhibits a purity of atleast 99 wt. %.

In the above-described manufacturing process, the chemical compoundselected in accordance with the invention is obtained in powdered formor in the form of a friable product which can be converted to powder.

An additional technical problem has been encountered, which resides inthat the product, if it is white, can turn yellow with time. This can beattributed to the fact that there may be an excess of iron, such as Fe(BF₄)₂, in the product. Unbonded iron Fe²⁺ has a tendency to oxidize inthe presence of water containing Fe³⁺.

The yellowing of the compound may adversely affect the contrast when thecompound is used in the manufacture of display devices and, in addition,oxidation may adversely affect the magnetic properties.

Consequently, the white colour must be stabilized in the finishedproduct. This is achieved by adding to the powder or to the friableproduct a quantity of less than 5% by weight of a reducing agent, suchas ascorbic acid.

When this method is used, all properties of the compound are preservedand the iron excess does not have an adverse effect. Consequently, theproduct indefinitely retains its perfectly white colour, even in thepresence of water, if certain temperature requirements, which will beexplained hereinbelow, are met.

III REMARKS

a) As stated hereinabove, it is not necessary for the network of themolecule of the compound in accordance with the invention to comprisewater. If said network comprises water, a ratio of one water molecule toone molecule of the compound is sufficient.

b) If, in the manufacturing process, instead of the compound comprising(BF₄ ⁻) as the anion, it is desired to provide a compound comprising oneof the other anions mentioned hereinabove, such as ClO₄ ⁻, CO₃ ²⁻, Br⁻,Cl⁻, the corresponding salt is used as the precursor of the ironnucleus, that is, respectively:

Fe(ClO₄)₂, 6H₂O

Fe(CO₃), 6H₂O

Fe(Br)₂, 6H₂O

Fe(Cl)₂, 6H₂O

and the process is continued in the same manner as with Fe(BF₄)₂, 6H₂Osalt.

c) In the manufacture of said compounds, other alcohol-like organicsolvents can be used instead of methanol.

IV GENERAL PROPERTIES OF SPIN-TRANSITION COMPOUNDS OF THE SUB-FAMILYSELECTED IN ACCORDANCE WITH THE INVENTION

With reference to FIG. 1, the compounds of the above-describedsub-family exhibit thermally induced spin transition phenomena.

These spin transitions are accompanied by electronic and structuralmodifications of the molecules. These modifications cause an abruptchange of the absorption spectrum of the molecules and hence of thecolour of the compounds due to the fact that the transitions between theelectronic energy levels have become different.

Thus, in the low-spin state (LS) the compounds are dark purple, whereasin the high-spin state (HS) the compounds are chalk-white. In these twostates the compounds exhibit a very great colour contrast.

Both the high-spin state and the low-spin state are stable at atemperature close to the so-called critical temperature. The high-spinand low-spin states are stable at this critical temperature in aconcomitant manner.

During the spin transitions, these materials exhibit a delay effectcaused by the intermolecular cooperativity. This brings about ahysteresis effect.

FIG. 1 shows that said compounds exhibit two potential wells, one ofwhich corresponds to curve A, which is related to the low-spin state,and the other corresponds to the curve B, which is related to thehigh-spin state. These potential wells A and B are separated by apotential barrier. The bottom Ao of the potential well A(LS) correspondsto a first energy level H_(LS) and to a first metal-ligand distanceD_(LS), and the bottom Bo of the potential well B(HS) corresponds to asecond energy level H_(HS) and to a second metal-ligand distance D_(HS).

The difference in energy between the bottom levels Ao and Bo of said twopotential wells is referred to as ΔH=H_(HS)−H_(LS).

An increase of the temperature of one of the selected compounds which,at the outset, is in the low-spin state (LS) in which the electrons aretrapped in the first potential well A induces excited high-spin states.However, these excited states are not stable and the electrons relaxback, via allowed transitions, while following a main relaxation pathwhich is that of the second potential well B, which corresponds to aperfectly stable high-spin state.

Consequently, the electrons remain trapped in the second potential wellB and do not spontaneously return to the first potential well A, whichcorresponds to the low-spin state. To return to the low-spin state, thecompounds must be cooled.

In FIG. 2, the curve a represents a hysteresis cycle of the compound ofthe formula

a) Fe(H-Trz)₃ (BF₄ ⁻)₂

which is directly obtained by the above-described method. Hereinbelow itwill be used as an exemplary compound.

The molar fraction X of the material which has undergone a transition ata temperature T (in degrees Kelvin) is plotted on the Y-axis and thetemperature T is plotted on the X-axis. The curve α of FIG. 2 shows thatthis compound has a hysteresis cycle in the range between:

T_(α1)=345 K for the high-spin transition temperature, and

T_(α2)=323 K for the low-spin transition temperature. At temperaturesbelow the temperature T_(α2), the compound is in the low-spin state(LS), and at temperatures above the temperature T_(α1), the compound isin the high-spin state (HS).

At a temperature T_(αc)≈334 K, being the mean critical temperature, thehigh-spin and low-spin states previously induced by a suitable thermalvariation remain stable for an indefinite period of time.

By virtue of the teachings of Patent Application EP 0 543 465, theseproperties were foreseen.

However, the selected compound a) exhibits remarkable effects under theconditions which will be described hereinbelow.

A first surprising effect is that if the compound of the formula a) isbrought to a temperature T which is higher than or equal to atemperature which is referred to as the first reference temperature

To=440 K

said compound undergoes a change in crystalline phase. The newcrystalline phase obtained by heating to a temperature which is higherthan or equal to To=440 K will hereinafter be referred to as crystallinephase β. The crystalline phase of the compound which is directlyobtained by the above method and of which the properties have beendescribed hereinabove is referred to as crystalline phase α.

A second, surprising effect is that the compound a) in its newcrystalline phase β also exhibits a spin transition with delay effect,but at different temperatures than in the crystalline phase α. This spintransition leads to the hysteresis cycle represented by curve β in FIG.2. In the crystalline phase β, this compound exhibits a hysteresis cyclewhich ranges between:

T_(β1)=282 K for the high-spin transition temperature, and

T_(β2)=276 K for the low-spin transition temperature.

In the low-spin state, the compound is purple in phase β as well as inphase α, whereas in the high-spin state, the compound is pure white.

Consequently, if use is made of a compound at an ambient temperatureT_(R)=290 K, referred to as second reference temperature, the compoundis in the low-spin state of phase a and of a purple colour, sinceT_(R)<T_(α2).

If the compound is heated to a temperature T, such that T_(α1)<T<To,i.e. 345 K<T<440 K, the compound turns white because it is in thehigh-spin state of phase α.

If the temperature is then lowered to the ambient temperature T_(R)=290°K, the compound turns purple again because it returns to the low-spinstate of phase α.

If the compound is then heated to a temperature in excess of the firstreference temperature To, i.e. higher than or equal to 440 K, thecompound turns white because it is in the high-spin state of phase β.

However, once the compound has been heated to a temperature above To,and its temperature is then reduced to the ambient temperature T_(R)=290K, the compound remains white: it remains in the high-spin state ofphase β because T_(R)>T_(β1).

The compound can be made purple again by cooling it to the low-spintransition temperature T_(β2) of phase β, i.e. it must be cooled to 276K or lower.

All of the selected compounds of the formulas a) to e) and a′) to e′)have the same properties and the same surprising effects as theabove-described compound a).

V DEVICE FOR WRITING, STORING AND DISPLAYING DATA

A device for writing, storing and displaying data, which comprises atleast one of the selected compounds in accordance with the invention isdescribed by way of example. This device comprises:

A) An Active Medium and a Support

To provide a device for writing, storing and displaying of data, it isfirst of all necessary to prepare an active medium which comprises oneor more spin-transition chemical compounds, as described hereinabove,and which medium is bonded to a support.

In a first example, the active medium can favourably be formed from athin film of the chemical compound which is directly deposited on thesupport. For this purpose, the film can be manufactured by evaporating asolvent which comprises the powder of the chemical compound selected.

In a second example, the chemical compound in powdered form can beembedded in a transparent material. This material may be a transparent,polymerizable resin which is deposited on the support.

The support may be a plate of any contour form or dimensions, such assquare, rectangular, polygonal, circular, oval, etc. In particular,plates of very large dimensions and very small dimensions can be used.The support may be rigid or flexible. In addition, a large number ofnon-brittle, low-cost materials, for example a synthetic material, canvery suitably be used as the support for the spin-transition compounds.

The device may be operated in the reflection mode or in the transmissionmode. If the device is operated in the transmission mode, the supportmay consist of a transparent synthetic material.

In the device for writing, storing and displaying, the active mediumcomprises display regions and background regions.

B) A Thermal Addressing System

The device must comprise, inter alia, means for locally changing thetemperature of the active medium or for changing the temperature of theentire active medium.

Said means consist of a thermal addressing system which serves to changethe temperature of the display regions and background regions.

B1) This thermal addressing system comprises, on the one hand, heatingmeans, such as:

a heating pencil, for example a laser beam in the infrared range of thespectrum or a laser having a wavelength of 520 mm or a pencil of theresistive-heating type,

a matrix of resistive-heating contacts which are addressed in accordancewith x, y-patterned lines and columns.

Said matrix of resistive-heating contacts may comprise two intersectingnetworks of electrodes. In a particular embodiment, the active mediummay be disposed between said two electrode networks, with aheat-dissipating system being provided. In a favourable embodiment, theelectrodes may be transparent and made, for example, of InSnO(indium-tin oxide). In this particular embodiment, the system forwriting, storing and displaying can operate equally well in thetransmission mode as in the reflection mode.

If the intended use does not require the electrodes to be transparent,they can be made of all metals which are customarily used for thispurpose.

The advantage of the system which includes a matrix of x,y electrodes isthat it can receive and display messages, data or informations which arecoded in x, y.

In accordance with the invention, the system made in this manner can forexample be used to realise an emission-reception device which is capableof displaying the transmitted message.

B2) This thermal addressing system comprises, on the other hand, coolingmeans, such as:

means for cooling the support as a whole,

means for locally cooling the support, such as Peltier elements whichare used to selectively cool the display regions or the backgroundregions.

VI METHOD OF EMPLOYING THESE DEVICES

FIG. 3 represents a device for writing, erasing and displayinginformation, which is produced by means of the compound a) describedhereinabove to form an active medium.

This device enables a screen consisting of a support covered with theactive medium containing the compound a) to be locally heated or cooledto various temperatures T_(α1), T_(α2), T_(R), T_(β1), T_(β2), To, in atleast one display region and one background region. In the exampleillustrated in FIG. 3, the screen comprises a single display regionwhich corresponds to a geometric pattern, in this case a letter of thealphabet “Z”.

Said heating and cooling means enable the following thermalperturbations to be successively, locally applied to the active mediumof this screen, in the displays region, at the location of the pattern:

A) The starting temperature is the ambient temperature T_(R)=290 K; thescreen is uniformly purple (FIG. 3A); the entire screen, i.e. thedisplay region and the background region, is in the low-spin state ofphase α.

B) The display area of the pattern is brought to a temperature T,

T_(α1)<T<To,

i.e. 345 K<T<440 K: the pattern is white on a purple background (FIG.3B); the area of the pattern is in the high-spin state of phase α; thebackground remains in the low-spin state of phase α.

C) The temperature of the area of the pattern is lowered to the ambienttemperature T_(R)=290 K, the screen becomes uniformly purple again (FIG.3C); the entire screen is in the low-spin state of phase α.

D) The area of the pattern is brought to the high temperature T which ishigher than or equal to To=440 K; the area of the pattern turns whitebecause it is in the high-spin state of phase β; the rest of the screenis purple because it remains in the low-spin state of phase α (FIG. 3D).

E) The area of the pattern is cooled to the ambient temperatureT_(R)=290 K; the area of the pattern remains white because it is stillin the high-spin state of phase β; the background of the screen remainspurple (FIG. 3E).

F) The temperature of the area of the pattern is reduced to atemperature which is lower than or equal to T_(β2)=276 K; the area ofthe pattern turns purple again (FIG. 3F).

The third surprising effect resides in that, despite the fact that thescreen has become entirely purple again the pattern is not erased: theinformation related to this pattern is only hidden. The background ofthe screen has remained in the low-spin state of phase a, while the areaof the pattern is in the low-spin state of phase β.

G) The area of the pattern is reheated to the ambient temperatureT_(R)=290 K, and as a result thereof the area of the pattern reappearsas a white-coloured part on a purple background because this area is nowin the high-spin state of phase β.

By virtue of these surprising novel properties of the compounds selectedin accordance with the invention, the information has been stored insteps D and E, hidden in step F and displayed again in step G (FIG. 3G).

H) the information which has reappeared in step G), in which step thearea of the pattern is in the high-spin state of phase β, isspontaneously erased after some time as a result of the fact that thecompound returns to phase α. This period of time varies and depends onwhich product from the list of selected products is used.

This period of time may be several hours or even several days. Thus,erasure takes place as a result of a spontaneous return from phase β tophase α.

The erasing operation can alternatively be induced at will by meansother than thermal means.

Thus, the compound is free of information again and can be used for anew writing step.

As already known, steps A, B and C enable the compound in phase a to beused for displaying information by determining the instant when theinformation is written and the instant when the information is totallyerased. The information can be stored in or originate from asupplementary device other than the active medium of the screen.Consequently, the active medium produced by means of the compound inphase α only has a display function.

Steps D to G enable the compound in phase β to display information,store said information in the active medium of the screen and,subsequently, hide said information and re-display it on the screen atany time. Consequently, in addition to the display function, the activemedium of the screen also has a storage function.

The above-described properties of the compound of the chemical formulaa) also apply to the other compounds b), c), d), e) and a′) to e′).

VII APPLICATIONS AND ADVANTAGES OF THE DEVICES FOR WRITING, STORING ANDDISPLAYING

A display device which has been produced by means of an active medium inaccordance with the invention can advantageously be used to manufacturea display screen for a smart card at very low cost. As describedhereinabove, the active medium may be bonded to a synthetic support,thereby forming a system which is particularly well suited to cooperatewith another synthetic support, such as the support of the smart card.In addition, the active medium bonded to its own support can beextremely thin. Consequently, the use of this active medium/supportsystem for the manufacture of a screen which can display the data storedin a smart card is very favourable.

Such a display system can also be used in many other devices in whichthe fragility of a screen of liquid crystals is unfavourable,particularly for displaying data concerning the functioning ofelectrodomestic appliances. The display device can also be used forcalculators, audio and video equipment, games etc., and in particularfor monitor screens, screens for the purposes of public address, urbansignposting, airport information posting etc. Such a display devicecould be used instead of a liquid crystal display device in a largenumber of applications, but it is not limited thereto, as it can bemanufactured on very large supports.

An application of the display system could be, for example, of the“magic tablet” type. This tablet is a device which employs a heatingpencil in combination with an active medium comprising the selectedcompounds. Such a magic tablet could be used to visualize the dataentered into an information storage device by means of a classic tactiletablet.

What is claimed is:
 1. A spin-transition parent compound in powder form,comprising a network having a molecule which is formed from a complex inwhich iron (Fe_(II)) is bonded to a 1-2-4 triazole ligand (H-Trz), saidmolecule further comprising an anion (A)₂ which is selected from BF₄ ⁻,ClO₄ ⁻, Cl⁻ , Br⁻, CO₃ ²⁻, and, dependent upon the anion, said moleculecorresponding to the formula: a′) Fe_(II)(H-Trz)₃ (BF₄ ⁻)₂, H₂O b′)Fe_(II)(H-Trz)₃ (ClO₄ ⁻)₂, H₂O c′) Fe_(II)(H-Trz)₃ (Br⁻)₂, H₂O d′)Fe_(II)(H-Trz)₃ (Cl⁻)₂, H₂O e′) Fe_(II)(H-Trz)₃ (CO₃ ²⁻), H₂O whereinone water molecule per molecule of the iron complex is present in thenetwork, said water molecule only being bonded to the 1-2-4 triazoleligand (H-Trz) by a hydrogen bond, and wherein said compound alsocomprises a hydroscopic salt in a quantity of from 25 to 100% of theweight of the compound, to ensure that said water molecule is present inthe network.
 2. A compound as claimed in claim 1, in which thehygroscopic salt is iron borofluoride, magnesium perchlorate, potassiumperchlorate, sodium perchlorate, or a mixture of said salts.
 3. Acompound as claimed in claim 2 comprising a reducing agent in a quantitybelow 5 wt. % of said compound.
 4. A compound as claimed in claim 1,comprising a reducing agent in a quantity below 5 wt. % of saidcompound.
 5. A compound as claimed in claim 4 wherein the reducing agentis ascorbic acid.
 6. A spin-transition parent compound in powder form,comprising a network having a molecule which is formed from a complex inwhich iron (Fe_(II)) is bonded to a 1-2-4 triazole ligand (H-Trz), saidmolecule further comprising an anion (A)₂ which is selected from BF₄ ⁻,ClO₄ ⁻, Cl⁻ , Br⁻, CO₃ ²⁻, and, dependent upon the anion, said moleculecorresponding to the formula: a) Fe_(II)(H-Trz)₃ (BF₄ ⁻)₂ b)Fe_(II)(H-Trz)₃ (ClO₄ ⁻)₂ c) Fe_(II)(H-Trz)₃ (Br⁻)₂ d) Fe_(II)(H-Trz)₃(Cl⁻)₂ e) Fe_(II)(H-Trz)₃ (CO₃ ²⁻) and wherein said compound furthercomprises a reducing agent in a quantity below 5 wt. % of said compound.7. A compound as claimed in claim 6, in which the reducing agent isascorbic acid.
 8. A spin-transition parent compound in powder form,comprising a network having a molecule which is formed from a complex inwhich iron (Fe_(II)) is bonded to a 1-2-4 triazole ligand (H-Trz), saidmolecule further comprising an anion (A)₂ which is selected from BF₄ ⁻,ClO₄ ⁻, Cl⁻ , Br⁻, CO₃ ²⁻, and, dependent upon the anion, said moleculecorresponding to the formula: a′) Fe_(II)(H-Trz)₃ (BF₄ ⁻)₂, H₂O b′)Fe_(II)(H-Trz)₃ (ClO₄ ⁻)₂, H₂O c′) Fe_(II)(H-Trz)₃ (Br⁻)₂, H₂O d′)Fe_(II)(H-Trz)₃ (Cl⁻)₂, H₂O e′) Fe_(II)(H-Trz)₃ (CO₃ ²⁻), H₂O whereinone water molecule per molecule of the iron complex is present in thenetwork, said water molecule only being bonded to the 1-2-4 triazoleligand (H-Trz) by a hydrogen bond, and wherein said compound furthercomprises a reducing agent in a quantity below 5 wt. % of said compound.